Mono and disazo compounds based on b-hydroxy-naphthoic acid derivatives or acetoacetarylide derivatives containing long-chain alkyl ester or alkylamide radicals

ABSTRACT

Compounds of formula I: ##STR1## wherein R is a radical of the formula --OR 3  or --NHR 3 , A is a radical of formula II or III: ##STR2## B is a radical of the formula ##STR3## n is the number 1 or 2, R 1  is --H or --Cl, R 2  is --H, halogen, --NO 2 , --CN, C 1  -C 4  alkyl, C 1  -C 4  alkoxy, --CF 3 , C 2  -C 5  alkoxycarbonyl or --CONH-phenyl, --NHCO-phenyl or phenoxy which is unsubstituted or substituted on the phenyl ring by one or two chlorine atoms or one or two methyl, methoxy or ethoxy groups, R 3  is alkyl containing at least 10 C atoms, R 4  and R 5  are each independently of the other --H, halogen, --NO 2 , --CN, --CF 3 , C 1  -C 4  alkyl or C 1  -C 4  alkoxy, R 6  is --H, --Cl, --Br, --CH 3  or --OCH 3  and X is --H, --Br, --OCH 3 , --CN or --NO 2 , are suitable as pigments, especially for coloring polyolefins, as well as novel intermediates of the formula ##STR4## wherein n is the number 1 or 2, R is a radical of the formula --OR 3  or --NHR 3 , R 1  is --H or --Cl, R 2  is --H, halogen, --NO 2 , --CN, C 1  -C 4  alkyl, C 1  -C 4  alkoxy, --CF 3 , C 2  -C 5  alkoxycarbonyl or --CONH-phenyl, --NHCO-phenyl or phenoxy which is unsubstituted or substituted on the phenyl ring by one or two chlorine atoms or one or two methyl, methoxy or ethoxy groups, R 3  is alkyl containing at least 10 C atoms, X is --H, --Br, --OCH 3 , --CN or --NO 2  and Q is --OH or halogen.

The present invention relates to novel disazo compounds containinglong-chain alkyl ester or alkylamide radicals and to their use forcoloring high-molecular organic material, especially polyolefins.

Azo pigments containing ester radicals have been known for a long time.Red disazo pigments have been disclosed e.g. in U.S. Pat. Nos. 3,137,688and 4689403, while yellow disazo compounds have been disclosed e.g. inU.S. Pat. Nos. 4,003,886 and 4,065,488. A main feature of the compoundslisted in said patents is the fact that they have at least four alkylester radicals, the alkyl radical containing up to a maximum of 4 Catoms. Monoazo pigments containing a lower alkyl ester radical are alsoknown, e.g. according to U.S. Pat. No. 4,392,999. Disazo pigmentscontaining alkylamide groups have been disclosed e.g. in U.S. Pat. No.3,562,249.

Although such products generally possess good pigment properties, theydo not always satisfy modern technological demands, e.g. because of lowheat stability and/or inadequate dispersibility.

It has now been found, surprisingly, that disazo pigments containing atleast two long-chain alkyl ester or alkylamide radicals are verysuitable for coloring high-molecular organic materials, especiallypolyolefins, said pigments having an improved dispersibility, a lowtendency to blooming and excellent pigment properties.

The present invention accordingly relates to compounds of formula I:##STR5## wherein R is a radical of the formula --OR₃ or --NHR₃, A is aradical of formula II or III: ##STR6## B is a radical of the formula##STR7## n is the number 1 or 2, R₁ is --H or --Cl, R₂ is --H, halogen,--NO₂, --CH, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, --CF₃, C₂ -C₅ alkoxycarbonylor --CONH-phenyl, --NHCO-phenyl or phenoxy which is unsubstituted orsubstituted on the phenyl ring by one or two chlorine atoms or one ortwo methyl, methoxy or ethoxy groups, R₃ is alkyl containing at least 10C atoms, R+and Rs are each independently of the other --H, halogen,--NO₂, --CN, --CF₃, C₁ -C₄ alkyl or C₁ -C₄ alkoxy, R₆ is --H, --Cl,--Br, --CH₃ or --OCH₃ and X is --H, --Br, --OCH₃, --CN or --NO₂.

Halogen in the groups listed above is fluorine, bromine or, inparticular, chlorine.

R₂, R₄ and R₅ as C₁ -C₄ alkyl are methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl or tert-butyl.

R₂, R₄ and R₅ as C₁ -C₄ alkoxy are e.g. methoxy, ethoxy. n-propoxy,isopropoxy, n-butoxy or tert-butoxy.

R₂ as C₂ -C₅ alkoxycarbonyl is e.g. methoxycarbonyl, ethoxycarbonyl,n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl ortert-butoxycarbonyl.

The radicals B in formulae II and III are derived fromm-phenylene-diamines and especially p-phenylenediamines of the followingformulae: ##STR8## wherein R₄ and R₅ are as defined above.

Examples of such diamines are: 1,4-diaminobenzene,1,4-diamino-2-chlorobenzene, 1,4-diamino-2-bromobenzene,1,4-diamino-2,5-dichloro-benzene, 1,4-diamino-2-methylbenzene,1,4-diamino-2,5-dimethylbenzene, 1,4-di- amino-2-methoxybenzene,1,4-diamino-2,5-dimethoxybenzene,1,4-diamino-5-methoxy-1,4-phenylenediamine,2-methyl-5-methoxy-1,4-phenylenediamine, 1,3-diaminobenzene,1,3-diamino-2-methylbenzene, 1,3-diamino-4-chlorobenzene and1,3-diamino-4-methylbenzene.

Examples of diamines derived from the radical of the formula ##STR9##are: 3,3'-dichlorobenzidine, 3,3'-dibromobenzidine,3,3'-dimethylbenzidine and 3,3'-dimethoxybenzidine.

Alkyl containing at least 10 C atoms (in the radical --OR₃ or --NHR₃) isbranched or linear alkyl, e.g. n-decyl, n-dodecyl, n-tridecyl,iso-tridecyl, n-tetradecyl (myristyl), n-pentadecyl, n-hexadecyl.1-methylpentadecyl, n-octadecyl, n-eicosyl, n-tetracosyl, n-hexacosyl,n-triacontyl or n-pentacontyl.

R₃ as alkyl is preferably C₁₂ to C₃₅ alkyl, especially C₁₂ to C₁₈ alkyl,or mixtures thereof, e.g. the mixtures of alcohols known and marketed asalfols, which have essentially alkyl groups containing the same numberof C atoms and are predominantly branched, and which are used asstarting materials. The alkyl groups in the alcohols are denoted by theterm "alfyl", e.g. alfyl-C₁₂ or alfyl-C₁₄.

Compounds of formula I in which formula I has the following structure:##STR10## and the groups R, R₁, R₂ and A are as defined above arepreferred.

Compounds of formula I in which formulae II and III have the followingstructures: ##STR11## and the groups R₄, R₅ and X are as defined aboveare also preferred.

Compounds of formula IV: ##STR12## wherein A is a radical of formula Vor VI: ##STR13## R is a radical of the formula --OR₃ or --NHR₃, R₂ is--H,

--CH₃, --OCH₃, --OC₂ H₅, --COOCH₃, --COOC₂ H₅ or --OC₆ H₅, R₃ is C₁₂-C₃₅ alkyl and R₄ and R₅ are independently of the other --H, --Cl,--CH₃, --OCH₃ or --OC₂ H₅. R is most preferably a radical of the formula--OR₃.

In formula IV, A is preferably a radical of formula V, especially aradical of formula V in which R₂ is --Cl, --CH₃ or --OCH₃, R₃ is C₁₂-C₁₈ alkyl and R₄ and R₅ are each independently of the other --H, --Cl,--CH₃ or --OCH₃.

The compounds of formula I are preferably symmetrical compounds, inwhich the two diazo components are identical. Asymmetrical compounds, inwhich the two diazo components are different, also come within thedefinition of formula I above.

The compounds of formula I can be prepared by processes known per se,e.g.:

(a) by condensing 2 mol of a carboxylic acid halide, especially achloride of the formula ##STR14## with a diamine of the formula H₂N--NH₂, especially H₂ N--B--NH₂, in particular ##STR15## e.g. accordingto U.S. Pat. No. 4,689,403, or by condensing 1 mol of a carboxylic acidhalide of the formula ##STR16## with 2 mol (where n=1) or 4 mol (wheren=2) of a long-chain alkyl-alcohol or alkylamine, e.g. according to U.S.Pat. No. 4,065,448, or

(b) by diazotizing an amine of the formula ##STR17## and then couplingthe resulting diazo component with a coupling component of the formula##STR18## e.g. according to U.S. Pat. No. 4,003,886, the groups n, B, R,R₁ to R₆, Hal and X being as defined above.

The above coupling components are known intermediates; on the otherhand, the carboxylic acid halides based on B-oxynaphthoic acid, andtheir corresponding acids, are novel intermediates. They can be obtainedby known processes, e.g. according to US patent no. 4689403.

The invention therefore further relates to compounds of the followingformula VII: ##STR19## wherein n is the number 1 or 2, R is a radical ofthe formula --OR₃ or --NHR₃, R₁ is --H or --Cl, R₂ is --H, halogen,--NO₂, --CN, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, --CF₃, C₂ -C₅ alkoxycarbonylor --CONH-phenyl, --NHCO--phenyl or phenoxy which is unsubstituted orsubstituted on the phenyl ring by one or two chlorine atoms or one ortwo methyl, methoxy or ethoxy groups, R₃ is alkyl containing at least 10C atoms, X is --H, --Br, --OCH₃, --CN or --NO₂ and Q is --OH or halogen,especially --Cl.

For the interpretation of C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₅alkoxycarbonyl and R₃, reference is made to the correspondingdefinitions already listed above.

Preferred compounds of formula VII have formula VIII: ##STR20## whereinR, R₁ and R₂ are as defined above.

Especially preferred compounds are those of formula VIII in which R₁ is--H, R₂ is --Cl, --CH₃ or --OCH₃ and R is a radical of the formula--OR₃, R₃ being C₁₂ -C₁₈ alkyl.

A preferred preparatory process is the condensation process according toscheme (a) above. The condensation is conveniently carried out in thepresence of an inert organic solvent under normal or over pressure, withor without a catalyst. Examples of suitable solvents are toluene,chlorobenzene, dichlorobenzenes such as o-dichlorobenzene,trichlorobenzenes, nitrobenzene or mixtures of aromatic and/or aliphaticsolvents, such as ®Shellsole.

However, the compounds of formula I can also be prepared via atransesterification or amidation reaction by transesterifying ortransamidating a compound of the formula ##STR21## wherein T is C₁ -C₃alkyl and the other radicals A, R₁ and R₂, and n, are as defined above,with an alcohol or an amine of the formula R₃ --OH or R₃ NH₂, by knownprocesses, to give compounds of formula I. T is methyl, ethyl, propyl orisopropyl.

The reaction is conveniently carried out direct in an excess of theappropriate long-chain alcohol or amine or in the presence of an organicsolvent, e.g. toluene, xylenes, dichlorobenzenes, nitrobenzene,chloronaphthalene, anisole, ®Dowtherm or ketones such as cyclohexanone,at elevated temperature, e.g. in the boiling range of the solvent used,under normal pressure or positive pressure, with or without catalysts.If catalysts are used, suitable examples are sulfuric acid,p-toluenesulfonic acid, methylsulfonic acid, LiH, LiNH₂, NaOCH₃,potassium tert-butoxide, tetraalkyltitanates, dibutyltin oxide or rareearths.

The resulting compounds of formula I are isolated in conventionalmanner, e.g. by filtration. The material on the suction filter is washedwith one of the solvents already indicated above and then convenientlywith water as well. Said compounds are generally obtained in good yieldand purity and can be used in finely divided form, without furtherpurification, e.g. for coloring high-molecular organic material.

If their purity and/or particle shape and size are not yet adequate oroptimum for use as pigments, the compounds of the present patentapplication can be conditioned further. Conditioning is understood asmeaning the production of a fine particle shape and size optimum for theapplication, for example by dry grinding with or without salt, bygrinding with solvent or water, by kneading with salt or by means of asubsequent heat treatment with solvent.

Heat treatments with solvents can be carried out e.g. in organicsolvents, preferably those with a boiling point above 100° C.

Solvents which prove particularly suitable for this purpose are benzenessubstituted by halogen atoms or alkyl or nitro groups, such as toluene,chlorobenzene, o-dichlorobenzene, xylenes or nitrobenzene, alcohols suchas isopropanol or isobutanol, ketones such as cyclohexanone, ethers suchas ethylene glycol monomethyl or monoethyl ether, amides such asdimethylformamide or N-methylpyrrolidone, and dimethyl sulfoxide,sulfolan or water by itself, if necessary under pressure. Theaftertreatment can also be carried out in water in the presence oforganic solvents and/or with the addition of surface-active substancesor aliphatic amines, or in liquid ammonia.

Depending on the conditioning process and/or intended application, itmay be advantageous to add certain amounts of texture-improving agentsto the compound of formula I of the present patent application, beforeor after the conditioning process. Suitable texture-improving agentsare, in particular, fatty acids containing at least 18 C atoms, forexample stearic or behenic acid, or amides or metal salts thereof,especially Mg salts, and plasticizers, waxes, resin acids such asabietic acid, rosin soap, alkylphenols or aliphatic alcohols such asstearyl alcohol, or vicinal diols such as dodecane-1,2-diol, as well asmodified rosin/maleate resins or fumaric acid/rosin resins. Thetexture-improving agents are preferably added in amounts of 0.1-30% byweight, especially 2-15% by weight, based on the end product.

High-molecular organic material can be of natural or synthetic origin.It can be e.g. natural resins or siccative oils, rubber or casein, ormodified natural substances such as chlorinated rubber, oil-modifiedalkyd resins, viscose or cellulose ethers or esters such as celluloseacetate, cellulose propionate, cellulose acetobutyrate ornitrocellulose, but in particular fully synthetic organic polymers(duroplasts and thermoplasts) such as those obtained by polymerization,polycondensation or polyaddition. Particular members from the class ofthe polymerization resins are: polyolefins such as polyethylene,polypropylene or polyisobutylene, and substituted polyolefins such aspolymers of vinyl chloride, vinyl acetate, styrene, acrylonitrile,acrylic and/or methacrylic acid esters or butadiene, as well ascopolymers of said monomers, especially ABS, EVA or acrylicacid/styrene/acrylonitrile (ASA).

Members from the class of the polyaddition resins and polycondensationresins are the condensation products of formaldehyde with phenols, i.e.phenoplasts, and the condensation products of formaldehyde with urea,thiourea and melamine, i.e. aminoplasts, the polyesters used as enamelresins, including both saturated resins, e.g. alkyd resins, andunsaturated resins, for example maleate resins, as well as linearpolyesters, polycarbonates, polyurethanes and polyamides or silicones.

Said high-molecular compounds can be used individually or in mixtures asplastic materials or melts, which can be spun into fibers if desired.

They can also be used in the polymerized state, in dissolved form, asfilm-forming agents or binders for enamels or printing inks, examplesbeing boiled linseed oil, nitrocellulose, alkyd resins, melamine resinsand urea/formaldehyde resins or acrylic resins.

The pigmentation of the high-molecular organic substances with thecompounds of formula I as defined is carried out for example by mixingsuch a compound, if desired in the form of masterbatches, with thesesubstrates using rolling mills, mixers or grinders. The pigmentedmaterial is then converted to the desired final form by processes knownper se, such as calandering, compression moulding, extrusion, coating,spinning, casting or injection molding. It is often desirable toincorporate so-called plasticizers into the high-molecular compoundsprior to shaping, in order to produce non-rigid molded articles or toreduce their brittleness. Examples of plasticizers which can be used areesters of phosphoric acid, phthalic acid or sebacic acid. Theplasticizers can be incorporated into the polymers before or after theincorporation of the pigment. As a further possibility, aimed atproducing different shades, fillers or other coloring constituents, suchas white, colored or black pigments, are also added to thehigh-molecular organic substances in any desired amounts, as well as thecompounds of the invention.

For pigmenting enamels and printing inks, the high-molecular organicmaterials and the compounds of formula I, if necessary together withadditives such as fillers, other pigments, siccatives or plasticizers,are finely dispersed or dissolved in a common organic solvent or solventmixture. This can be done by dispersing or dissolving the individualcomponents separately, or else several together, and only then bringingall the components together.

The compositions of substances of the present patent applicationpreferably contain 0.01-20% by weight of a compound of formula I asdefined, for example in plastics, fibers, enamels and prints, and aredistinguished by good dispersibility, good resistance to overcoating,migration, heat, light and weather. good color strength and a goodgloss.

However, the compounds of formula I are preferably used for coloringpolyolefins.

Examples of polyolefins are high and low density polyethylene (HD-PE,LD-PE and LLD-PE), polypropylene and polyisobutylene, as well ascopolymers of polyolefins with e.g. polyethers, polyether-ketones orpolyurethanes.

Coloring is carried out by conventional processes, for example by mixinga compound of formula I with the polyolefin granules or powder andextruding the mixture to form fibers, sheets or granules. The latter canthen be shaped into articles by injection moulding.

The colorings obtained exhibit high purity and high saturation and aredistinguished by an excellent dispersibility, by good general resistanceproperties, especially to heat and light, and by their low tendency toblooming. A particular advantage of polyethylene articles colored withthe compounds of formula I of the invention is that they do not have anincreased susceptibility to distortion and deformation phenomena,especially in the case of HD-PE. They additionally exhibit a high acidresistance.

The plastic fibers mass-colored with the compounds of formula I of theinvention, e.g. PP fibers, possess excellent textile properties such aslight stability and wet resistance to detergents and solvents.

The following Examples will serve to illustrate the invention.

EXAMPLE 1A

18 g of the azo dye formed from diazotized stearyl4-methyl-3-aminobenzoate and 2-hydroxy-3-naphthoic acid are suspended in150 g of anhydrous toluene. 4.9 g of thionyl chloride and 6 drops ofdimethylformamide are added to the mixture, which is heated at 67° to68° C. for one hour, with stirring. The dark solution is concentrated todryness under vacuum. The resulting product is then removed from theflask with 50 ml of petroleum ether, isolated by suction filtration anddried under vacuum at 50° C. to give 16.95 g (91% of theory) of the azodye carboxylic acid chloride of the formula ##STR22## which melts at107° to 108° C.

Combustion analysis

Calc. (in %): C 71.53, H 7.95, Cl 5.71, N 4.51;

Found (in %): C 71.82, H 8.07, Cl 5.29, N 4.45.

14.25 g of the dye acid chloride prepared in this way are stirred with160 g of anhydrous o-dichlorobenzene and heated to 80° C. The clear,dark red solution is treated at this temperature with a warm solution,at 70° C., of 2.05 g of 2,5-dichloro-1,4-phenylenediamine in 150 ml ofo-dichlorobenzene, producing a red precipitate. The red suspensionformed is heated to 120° C., with stirring, and stirring is continuedfor 16 hours at this temperature. The product is isolated hot by suctionfiltration and washed with warm o-dichlorobenzene and then with hotmethanol. Drying of the product under vacuum at 60° C. gives 14.1 g(91.5% of theory) of a soft-grained red powder which colors e.g.polyethylene, polyvinyl chloride and polyamide in intense red shades ofexcellent heat and light stability. The pigment has the followingstructure: ##STR23## and gives the following combustion analysis: Calc.(in %): C 71.35, H 7.64, Cl 5.27, N 6.24;

Found (in %): C 71.29, H 7.65, Cl 5.43, N 6.17.

EXAMPLE 1B

If the procedure is the same as in the above Example, except that theazo dye carboxylic acid chloride indicated in said Example is replacedwith a corresponding amount of the azo dye carboxylic acid chloride ofthe formula ##STR24## and the 2,5-dichloro-1,4-phenylenediamine isreplaced with a corresponding amount of2,5-dimethyl-1,4-phenylenediamine, a red powder of the followingformula: ##STR25## is obtained.

Combustion analysis

Calc. (in %): C 75.54, H 8.50, N 8.59;

Found (in %): C 75.19, H 8.48, N 8.56.

EXAMPLES 2-37

The following Table contains further pigments which can be prepared bythe process of Example 1 above by coupling the diazo compound of theamines listed in column I with 2-hydroxy-3-naphthoic acid, convertingthe resulting azo dye carboxylic acid into the corresponding acidchloride and condensing the latter with the diamines indicated in columnII in a molar ratio of 2:1. Column III characterizes the shade of thepolyvinyl chloride sheet colored with the resulting pigments accordingto Example 63.

    ______________________________________                                        Ex.    I                II          III                                       ______________________________________                                         2   stearyl 4-methyl-3-amino-                                                                      2,5-dimethyl-p-                                                                             scarlet                                        benzoate         phenylenediamine                                         3   stearyl 4-methyl-3-amino-                                                                      p-phenylenediamine                                                                          scarlet                                        benzoate                                                                  4   stearyl 4-methyl-3-amino-                                                                      2-chloro-p-   red                                            benzoate         phenylenediamine                                         5   stearyl 4-methyl-3-amino-                                                                      2-chloro-5-methyl-                                                                          scarlet                                        benzoate         p-phenylenediamine                                       6   stearyl 4-methyl-3-amino-                                                                      2,5-dimethoxy-p-                                                                            claret                                         benzoate         phenylenediamine                                         7   stearyl 4-aminobenzoate                                                                        2,5-dimethyl-p-                                                                             reddish                                                         phenylenediamine                                                                            brown                                      8   distearyl 2-amino-                                                                             2,5-dimethyl-p-                                                                             yellowish                                      terephthalate    phenylenediamine                                                                            brown                                      9   stearyl 3-aminobenzoate                                                                        2,5-dichloro-p-                                                                             reddish                                                         phenylenediamine                                                                            orange                                    10   stearyl 3-aminobenzoate                                                                        2,5-dimethoxy-p-                                                                            brown                                                           phenylenediamine                                        11   stearyl 3-aminobenzoate                                                                        2-chloro-5-methyl-                                                                          orange                                                          p-phenylenediamine                                      12   stearyl 4-chloro-3-amino-                                                                      p-phenylenediamine                                                                          yellowish                                      benzoate                       brown                                     13   stearyl 4-chloro-3-amino-                                                                      2,5-dichloro-p-                                                                             scarlet                                        benzoate         phenylenediamine                                        14   stearyl 4-chloro-3-amino-                                                                      2,5-dimethyl-p-                                                                             red                                            benzoate         phenylenediamine                                        15   stearyl 4-chloro-3-amino-                                                                      2-chloro-5-methyl-                                                                          red                                            benzoate         p-phenylenediamine                                      16   stearyl 4-chloro-3-amino-                                                                      2,5-dimethoxy-p-                                                                            brown                                          benzoate         phenylenediamine                                        17   stearyl 4-chloro-3-amino-                                                                      p-phenylenediamine                                                                          carmine                                        benzoate                                                                 18   stearyl 4-methoxy-3-amino-                                                                     2,5-dichloro-p-                                                                             scarlet                                        benzoate         phenylenediamine                                        19   stearyl 4-methoxy-3-amino-                                                                     2,5-dimethyl-p-                                                                             carmine                                        benzoate         phenylenediamine                                        20   stearyl 4-methoxy-3-amino-                                                                     2-chloro-5-methyl-                                                                          carmine                                        benzoate         p-phenylenediamine                                      21   stearyl 4-methoxy-3-amino-                                                                     2,5-dimethoxy-p-                                                                            red                                            benzoate         phenylenediamine                                        22   n-decanyl 4-methyl-3-                                                                          2,5-dichloro-p-                                                                             red                                            aminobenzoate    phenylenediamine                                        23   n-decanyl 4-methyl-3-                                                                          2,5-dimethyl-p-                                                                             red                                            aminobenzoate    phenylenediamine                                        24   n-decanyl 4-methyl-3-                                                                          2,5-dimethoxy-p-                                                                            dark red                                       aminobenzoate    phenylenediamine                                        25   n-decanyl 4-methyl-3-                                                                          2-chloro-5-methyl-                                                                          red                                            aminobenzoate    p-phenylenediamine                                      26   n-tetradecanyl 4-methyl-                                                                       2,5-dichloro-p-                                                                             carmine                                        3-aminobenzoate  phenylenediamine                                                                            red                                       27   n-tetradecanyl 4-methyl-                                                                       2,5-dimethyl-p-                                                                             red                                            3-aminobenzoate  phenylenediamine                                        28   lauryl 4-methyl-3-amino-                                                                       2,5-dichloro-p-                                                                             red                                            benzoate         phenylenediamine                                        29   lauryl 4-methyl-3-amino-                                                                       2,5-dimethyl-p-                                                                             red                                            benzoate         phenylenediamine                                        30   stearyl 4-methyl-3-amino-                                                                      1,5-diamino-naph-                                                                           carmine                                        benzoate         thalene                                                 31   stearyl 4-methoxy-3-amino-                                                                     1,5-diamino-naph-                                                                           carmine                                        benzoate         thalene                                                 32   n-decanyl 4-methyl-3-                                                                          1,5-diamino-naph-                                                                           carmine                                        aminobenzoate    thalene                                                 33   n-tetradecanyl 4-methyl-3-                                                                     1,5-diamino-naph-                                                                           carmine                                        aminobenzoate    thalene                                                 34   stearyl 4-methyl-3-amino-                                                                      3,3'-dichloro-ben-                                                                          orange                                         benzoate         zidine                                                  35   stearyl 4-methoxy-3-amino-                                                                     3,3'-dichloro-ben-                                                                          red                                            benzoate         zidine                                                  36   stearyl anthranilate                                                                           2,5-dichloro-p-                                                                             orange                                                          phenylenediamine                                        37   lauryl anthranilate                                                                            2,5-dichloro-p-                                                                             orange                                                          phenylenediamine                                        ______________________________________                                    

EXAMPLE 38

3.55 g of the disazo dicarboxylic acid dichloride of the formula##STR26## and 8.8 g of stearyl alcohol (97%) are heated to 140° C. in200 g of o-dichlorobenzene and stirred at this temperature for 6 hours,during which time the reddish brown suspension dissolves. The turbidbrown solution formed is cooled to 100° C. and filtered hot. There ispractically no residue. The filtrate produces a yellow precipitate. 120g of 96% ethyl alcohol are added and the product is isolated by suctionfiltration. It is washed with 150 g of 96% ethyl alcohol and dried undervacuum at 60° C. to give 5.4 g (92.6% of theory) of an intense yellowpowder of the formula ##STR27##

Analysis

Calc. (in %): C 67.50, H 8.41, Cl 6.04, N 7.16;

Found (in %): C 67.35, H 8.35, Cl 6.25, N 7.16.

The product of this Example colors polyethylene, polyamide and polyvinylchloride in intense yellow shades of excellent heat and light stability.

EXAMPLES 39-44

The Table below describes further compounds which can be prepared by theprocess of Example 1 by coupling the diazo compound of the amines listedin column I with the bis-acetoacetic acid arylide of the diamines listedin column II, converting the resulting disazo dye dicarboxylic acid intoits corresponding dicarboxylic acid dichloride and then condensing thelatter with stearyl alcohol. Column III indicates the shade of the PVCsheet colored with these pigments.

    ______________________________________                                        Ex.    I             II             III                                       ______________________________________                                        39   4-chloro-3-amino-                                                                           p-phenylenediamine                                                                             greenish                                       benzoic acid                   yellow                                    40   4-chloro-3-amino-                                                                           2-chloro-p-phenylenedi-                                                                        greenish                                       benzoic acid  amine            yellow                                    41   4-methoxy-3-amino-                                                                          2,5-dimethyl-p-phenylene-                                                                      yellow                                         benzoic acid  diamine                                                    42   4-chloro-3-amino-                                                                           2-chloro-5-methyl-p-                                                                           greenish                                       benzoic acid  phenylenediamine yellow                                    43   4-chloro-3-amino-                                                                           2,5-dichloro-p-phenylene-                                                                      greenish                                       benzoic acid  diamine          yellow                                    44   4-methyl-3-amino-                                                                           2,5-dimethyl-p-phenylene-                                                                      yellow                                         benzoic acid  diamine                                                    ______________________________________                                    

EXAMPLE 45

4.7 g of stearyl 4-chloro-3-aminobenzoate and 1.9 g of3,3'-dimethyl-4,4'-diacetoacetylaminobiphenyl are heated to 63° C. in200 g of acetic acid. The clear yellow solution formed is cooled to 53°C. and 2.86 ml of a 4 N sodium nitrite solution are quickly addeddropwise at this temperature, producing a thick orange precipitate. Theorange suspension is stirred for 3 hours at 56° C., cooled to roomtemperature and filtered. The material on the suction filter is washedwith 200 g of 96% ethyl alcohol and dried under vacuum at 60° C. to give5.8 g (93.55% of theory) of a yellowish orange powder of the formula##STR28##

Analysis

Calc. (in %): C 69.15, H 8.22, Cl 5.67, N 6.72;

Found (in %): C 69.43, H 8.23, Cl 5.433, N 6.61.

This product colors polyethylene, polyamide and polyvinyl chloride inintense yellow shades. These colorings have excellent heat and lightstability.

EXAMPLES 46-61

The Table below describes further compounds which ar obtained bycoupling the diazo compound of the bases listed in column I with thebis-acetoacetic acid arylide of the diamines listed in column II in amolar ratio of 2:1. Column III indicates the shade of the PVC sheetcolored with these pigments.

    ______________________________________                                        Ex.    I                 II         III                                       ______________________________________                                        46   4-chloro-3-amino-benzoic-                                                                       2,5-dimethyl-p-                                                                            yellow                                         acid stearylamide phenylenediamine                                       47   stearyl 4-methyl-3-amino-                                                                       p-phenylenedi-                                                                             greenish                                       benzoate          amine        yellow                                    48   stearyl 3-aminobenzoate                                                                         2,5-dimethyl-p-                                                                            greenish                                       stearylester      phenylenediamine                                                                           yellow                                    49   stearyl 2,4-dichloro-3-                                                                         2,5-dimethyl-p-                                                                            greenish                                       aminobenzoate     phenylenediamine                                                                           yellow                                    50   stearyl 4-phenoxy-3-amino-                                                                      2,5-dimethyl-p-                                                                            orange-                                        benzoate          phenylenediamine                                                                           yellow                                    51   stearyl 5-nitro-3-amino-                                                                        2,5-dimethyl-p-                                                                            orange                                         benzoate          phenylenediamine                                       52   stearyl 4-chloro-3-amino-                                                                       2,5-diethoxy-p-                                                                            orange                                         benzoate          phenylenediamine                                       53   n-decanyl 4-methyl-3-                                                                           2,5-dimethyl-p-                                                                            yellow                                         aminobenzoate     phenylenediamine                                       54   lauryl 4-methyl-3-amino-                                                                        2,5-dimethyl-p-                                                                            yellow                                         benzoate          phenylenediamine                                       55   n-tetradecanyl 4-methyl-3-                                                                      2,5-dimethyl-p-                                                                            yellow                                         aminobenzoate     phenylenediamine                                       56   stearyl 4-chloro-3-amino-                                                                       3,3'-dichloro-                                                                             greenish                                       benzoate          benzidine    yellow                                    57   stearyl 4-chloro-3-amino-                                                                       3,3'-dimethoxy-                                                                            orange                                         benzoate          benzidine                                              58   stearyl 4-chloro-3-amino-                                                                       2,5-diamino- yellow                                         benzoate          naphthalene                                            59   stearyl 4-amino-benzoate                                                                        2,5-dimethyl-p-                                                                            orange                                                           phenylenediamine                                       60   distearyl 2-amino-                                                                              p-phenylene-di-                                                                            yellow                                         terephthalate     amine                                                  61   distearyl 2-amino-                                                                              2,5-dimethyl-p-                                                                            yellow                                         terephthalate     phenylenediamine                                                                           orange                                    ______________________________________                                    

EXAMPLE 62

A mixture of 1.0 g of the disazo condensation pigment obtained accordingto Example 1A, 1.0 g of the antioxidant ®IRGANOX 1010 (CIBA-GEIGY AG)and 1000 g of polyethylene HD granules (®VESTOLEN A60-16, HUELS) ispremixed for 15 minutes in a 3 1 glass flask on a roller gear bed. Themixture is then extruded twice through a single-screw extruder. Theresulting granules are then converted to plates on an injection moldingmachine (®Allround Aarburg 200) at 250° C. with a dwell time of 5minutes. The resulting plates have uniformly intense, bluish redcolorations of high purity and excellent light stability.

EXAMPLE 63

40 mg of the disazo condensation pigment obtained according to ExamplelA are mixed thoroughly with 7.3 ml of dioctyl phthalate and 13.3 g of astabilized polyvinyl chloride of the ®LONZA E-722 type in a glass beakerusing a glass rod. The mixture obtained is then processed on a rollermill for 5 minutes at 160° C. to form a thin sheet. The PVC sheetproduced exhibits a very intense, bluish red coloration of high purityand very good light stability. The pigment has excellent dispersibility.

By an analogous procedure, the pigments obtained according to theinvention in Examples 2 to 61 can also be used to color PVC, resultingin equally good properties.

EXAMPLE 64

1000 g of polypropylene granules (®DAPLEN PT-55, Chemie LINZ) and 1.0 gof the disazo condensation pigment obtained according to Example 1A aremixed for 15 minutes in a 3 1 flask on a roller gear bed. The mixture isthen extruded twice through a single-screw extruder and subsequentlygranulated. The resulting granules are melt-spun at 280°-285° C. Thefibers colored in this way have a very good light stability andexcellent textile fastness properties such as fastness to rubbing andwet fastness to detergents and solvents. The pigment has excellent heatstability during the spinning process at 285° C.

EXAMPLE 65

100 g of the polyamide ®GRILON A 25 (EMS-Chemie AG, Zurich) and 0.2 g ofthe disazo condensation pigment obtained according to Example 1A aremixed thoroughly on a laboratory turbomixer (W. A. Bachofen, Basle) for20 minutes. The mixture is then extruded on a single-screw extruder at240° C. The resulting ribbon has a red coloration and exhibits goodlight stability properties.

EXAMPLE 66

If the procedure is analogous to that described in Example 62, exceptthat 10 g of the titanium dioxide ®KRONOS RN-57-P (KRONOS Titan GmbH)are used in addition to the colored pigment, red plates with equallygood heat stability properties are obtained. The plates injection-moldedin the temperature range from 200° to 280° C. do not exhibit any colorvariations after cooling.

What is claimed is:
 1. A compound of formula I: ##STR29## wherein R is aradical of the formula --OR₃ or --NHR₃, A is a radical of formula II orIII: ##STR30## B is a radical of the formula ##STR31## n is the number 1or 2, R₁ is --H or --Cl, R₂ is --H, halogen, --NO₂, --CN, C₁ -C₄ alkyl,C₁ -C₄ alkoxy, --CF₃, C₂ -C₅ alkoxycarbonyl or --CONH-phenyl,--NHCO-phenyl or phenoxy which is unsubstituted or substituted on thephenyl ring by one or two chlorine atoms or one or two methyl, methoxyor ethoxy groups, R₃ is alkyl containing at least 10 C atoms, R₄ and R₅are each independently of the other --H, halogen, --NO₂, --CN, --CF₃, C₁-C₄ alkyl or C₁ -C₄ alkoxy, R₆ is --H, --Cl, --Br, --CH₃ or --OCH₃ and Xis --H, --Br, --OCH₃, --CN or --NO₂.
 2. A compound of formula Iaccording to claim 1 in which formula I has the following structure:##STR32## and the groups R, R₁, R₂ and A are as defined in claim
 1. 3. Acompound of formula I according to claim 1 in which formulae II and IIIhave the following structures: ##STR33## and the groups R₄, R₅ and X areas defined in claim
 1. 4. A compound of formula IV according to claim 1:##STR34## wherein A is a radical of formula V or VI: ##STR35## R is aradical of the formula --OR₃ or --NHR₃, R₂ is --H, --Cl, --CH₃, --OCH₃,--OC₂ H₅, --COOCH₃, --COOC₂ H₅ or --OC₄ H₅, R₃ is C₁₂ -C₃₅ alkyl and R₄and R₅ are each independently of the other --H, --Cl, --CH₃, --OCH₃ or--OC₂ H₅.
 5. A compound of formula IV according to claim 4 in which R isa radical of the formula --OR₃.
 6. A compound of formula IV according toclaim 4 in which A is a radical of formula V.
 7. A compound of formulaIV according to claim 4 in which A is a radical of formula V, R₂ is--Cl, --CH₃ or --OCH₃, R₃ is C₁₂ -C₁₈ alkyl and R₄ and R₅ are eachindependently of the other --H, --Cl, --CH₃ or --OCH₃.
 8. A compound offormula VII: ##STR36## wherein n is the number 1 or 2, R is a radical ofthe formula --OR₃ or --NHR₃, R₁ is --H or --Cl, R₂ is --H, halogen,--NO₂, --CN, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, --CF₃, C₂ -C₅ alkoxycarbonylor --CONH-phenyl, --NHCO-phenyl or phenoxy which is unsubstituted orsubstituted on the phenyl ring by one or two chlorine atoms or one ortwo methyl, methoxy or ethoxy groups, R₃ is alkyl containing at least 10C atoms, X is --H, --Br, --OCH₃, --CN or --NO₂ and Q is --OH or halogen.9. A compound according to claim 8 in which Q is --Cl.
 10. A compoundaccording to claim 8 in which formula VII has structure VIII: ##STR37##wherein R, R₁ and R₂ are as defined in claim
 8. 11. A compound accordingto claim 10 in which R₁ is --H, R₂ is --Cl, --CH₃ or --OCH₃ and R is aradical of the formula --OR₃, R₃ being C₁₂ -C₁₈ alkyl.